US5386804A - Process for the addition of ferrocene to combustion or motor fuels - Google Patents
Process for the addition of ferrocene to combustion or motor fuels Download PDFInfo
- Publication number
- US5386804A US5386804A US07/978,755 US97875592A US5386804A US 5386804 A US5386804 A US 5386804A US 97875592 A US97875592 A US 97875592A US 5386804 A US5386804 A US 5386804A
- Authority
- US
- United States
- Prior art keywords
- ferrocene
- combustion
- sublimator
- carrier gas
- gas stream
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Definitions
- the invention relates to a process for the addition of ferrocene to combustion or motor fuels in order to improve their combustion with atmospheric oxygen or oxygen-containing gases.
- liquid hydrocarbon mixtures comprising in essence gasoline and an organometallic compound from the group of [bis( ⁇ -cyclopentadienyl)-iron], called ferrocene in the following, and gasoline-soluble derivatives of ferrocene have been proposed (see DE-OS 25 02 307).
- German patent application P 41 29 408 a device and a process for the direct addition of a solid additive--ferrocene--to liquid motor fuels have been proposed, where, controlled by means of pulverizing ferrocene compacts, ferrocene is added to the liquid fuel in metered amounts.
- an object of the present invention is to enable an improved metering of the additive ferrocene into the combustion chamber of a combustion engine or an oil-fired heating system without the preceding admixture as solid or as stock solution to the combustion fuel, motor fuel or lubricant.
- the problem is solved by conveying vaporous ferrocene through sublimation into a stream of the combustion gas or a substream thereof and by feeding with the combustion or motor fuel, which is present as a vapor or finely distributed as solid or liquid particles, to the chemical conversion through combustion.
- the advantageous solution of the problem is based thus on the utilization of the sublimation properties of ferrocene.
- This measure offers the advantage that the amount of ferrocene can be readily adjusted with standard measures to the optimally required quantities for the individual different operating states of internal combustion engines.
- the compacts or pellets made of ferrocene crystals have dimensions of preferably 1 to 10 mm and are admitted into a sublimator with a carrier gas stream of the combustion gas or by parts of a combustion gas at pressure and temperature values in the range of the interface or coexistence line between the solid and gaseous phase.
- the ferrocene-containing carrier gas stream is led from there on into the combustion chamber.
- Ferrocene is a substance, which precipitates as yellow-orange needles depending on the manufacturing method.
- Moldings made of commercially manufactured ferrocene such as pellets, compacts or chips having dimensions ranging from 1 to 10 mm can be received advantageously in a suitable vessel of the sublimator.
- the ferrocene compacts can be made of ferrocene crystals (purity at least 98.5% by wt.), originating from a crystallizing solution, and wetted with solvent, for example, wetted with ethanol, without the addition of binders or the like.
- the combustion air functioning as the carrier gas stream can be preheated to a temperature ranging from 20° to 175°, preferably from 50° to 150° C.
- operating states of the sublimator can range, depending on how it is fixed structurally into the engine space or in the space adjacent to the burner of a heater, from about minus 40° C. at cold outer temperatures and unprotected location up to plus 50° C. with suitable heating by means of the burner or engine operation.
- additional heating for the sublimator, a feature that contributes to the uniformity of the operating behavior even at the start of putting into service.
- the pressure prevailing in the sublimator owing to the pressure of the carrier gas stream ranges preferably from 100 mbar to 3 bar.
- the pressure and temperature conditions and the geometric dimensions of the sublimator and the quantity of carrier gas can be specified in such a manner that an evaporated quantity of ferrocene ranging from 0.1 to 1,000, preferably from 1 to 100 mg per kg of combustion or motor fuel is produced.
- a preferred operating mode is to preheat the carrier gas stream to a temperature ranging from 20° to 175°, preferably from 50° to 150° C.
- One application of the present process relates to introducing a ferrocene-containing carrier gas stream into the combustion chamber of a diesel engine.
- the exhaust gas side of the diesel engine can be equipped with a particulate filter to retain carbon-containing particles contained in the exhaust gas, called by the expert particulates, which stem from the incomplete combustion of the diesel fuel with the combustion air in the engine.
- FIG. 1 shows an arrangement for charging a carrier gas stream with ferrocene
- FIG. 2 shows a further embodiment for charging ferrocene
- FIG. 3 shows a graph illustrating the burn-off behavior of a diesel particulate filter in a test conducted for 20 hours
- FIG. 4 shows a further long time test on the burning behavior of the diesel particulate filter
- FIG. 5 shows comparison test data with respect to the suppression of knocking according to the present invention.
- FIG. 1 shows an arrangement in which a carrier gas stream is fed from an intake air pipe and is led by way of a sublimator 9, which is charged with compacts made of ferrocene and integrated into a motor vehicle engine 3.
- the sublimator 9 is disposed upstream of an air filter 5 for the combustion air sucked in by the diesel engine.
- the venting of the crankcase is connected, as normal, downstream of the air filter to the pipe of the combustion air.
- Points 1 and 2 denote the measuring point for the temperature in the sublimator 9 or the temperature and the pressure upstream of a diesel particulate filter 11.
- FIG. 2 shows another modification for bringing in ferrocene.
- FIGS. 1 and 2 are designed in detail to the effect that the carrier gas stream branches off from the intake air pipe provided in each motor vehicle engine or from the venting of the crankcase and is led in such a manner from there into the sublimator 9 loaded with received ferrocene pellets that a passage of the ferrocene vapor into the carrier vapor stream is brought about.
- the passage being as complete as possible under the selected pressure and temperature conditions.
- the ferrocene-loaded carrier gas stream is united with the requisite amount of intake air downstream of the intake air filter 5 while avoiding condensation and led to the combustion chamber of the engine 3.
- the exhaust gas from the combustion of the fuel is released downstream of the engine by way of the particulate filter 11 and a muffler 15 into the atmosphere.
- Points 1 and 2 denote the measuring points for the temperature in the sublimator 9 or for the temperature and the pressure before the combustion exhaust gases enter into the particulate filter 11.
- the graph according to FIG. 3 shows the results, obtained with such an arrangement, namely a sublimator filled with ferrocene pellets in the venting of the crankcase, with respect to the burn-off behavior of the diesel particulate filter in a long time test conducted for 20 hours.
- test engine was operated with combustion air to which an additive had been added by way of the venting of the crankcase.
- the lubricant used belonged to the class SAE 15 W 40.
- test engine was a model of the manufacturer Opel 2.3 liter car engine, having free intake with swirl type combustion process and a nominal output of 54 kw.
- the engine was run at 2,000 rpm and a load of 28 Nm torque (partial load).
- the temperature in the sublimator was about 40° C.
- the dotted curve denotes the measured values of the temperature at the measurement point 2 in front of the diesel particulate filter 11.
- the solid, saw-toothed curve reproduces the change in the pressure upstream of the diesel particulate filter 11.
- the pressure builds up from about 80 to 350 mbar on account of the deposit of carbon-containing particles in the combustion exhaust gas on the filter up to an operating period of about 7 hours.
- the diesel particulate filter 11 is regenerated by burning off the particulates collected in the filter, thus reducing the pressure to about 50 mbar.
- an exhaust gas back pressure builds up again in accordance with the loading of the filter caused by the particulate emission of the diesel engine; then upon reaching values of about 200 to max, 350 mbar after a cycle time of about 2 to 3 hours, there is spontaneous burning, so that in total the operating behavior of the engine was acceptable over the run time.
- FIG. 4 shows a long time test on the burning behavior of diesel particulate filter 11 under conditions comparable to those on which the diagram of FIG. 3 is based, with the single difference that no additive was added to the combustion air by means of a carrier gas stream from the venting of the crankcase.
- the arrangement also includes the sublimator 9 as shown in FIG. 2, but the sublimator was not charged with ferrocene pellets.
- the dotted curve shows the plotting of the temperature at measuring point 2 according to FIG. 2 upstream of the diesel particulate filter 11. It is apparent that here a slow, but constant rise from about 190° to about 280° C. was observed.
- the solid line shows an almost linear rise of the exhaust gas back pressure upstream of the diesel particulate filter 11 measured at measuring point 2 according to FIG. 2.
- the exhaust gas back pressure had reached a value of 800 mbar, a value that does not in any way enable any more an acceptable operation of the engine.
- the test was therefore terminated. Even though the temperature at the measuring point 2 according to FIG. 2 had reached a value of about 280° C. at the instant the test was terminated, no burn-off of the diesel particulate filter 11 had taken place, whereas, according to the results according to FIG. 3, when ferrocene was added according to the invention, a burn-off took place at temperatures, measured at the same measuring point, of about 220° C.
- the introduction of the carrier gas stream to which ferrocene is added into the combustion chamber significantly improves in Otto and Wankel engines with and without subsequent catalyst for the afterburning of the exhaust gas the combustion behavior in the engine, which is driven with commercially available motor fuels.
- the occurrence of knocking in the engine is significantly suppressed.
- the power output of the engine can be increased.
- the fuel consumption is reduced through the effect of the additive.
- ferrocene acts as a wear-reducing component at the exhaust valve seat.
- the regenerability of a diesel particulate filter following a diesel engine is improved or enabled without additional devices to increase the temperature or to introduce operations to a periodic burning of the carbon-containing particles (diesel particulates) collecting on the filter for the purpose of maintaining low acceptable values for the pressure drop downstream of the filter.
Abstract
Description
______________________________________ formula Fe(C.sub.5 H.sub.5).sub.2 mole mass 186.04 g/mo.sup.1 density 1.49 g/cm.sup.3 melting point 173° C. boiling point 249° C. 1.035 bar shrivel point 183° C. vapor pressure 0.666 mbar 40° C. 3.4mbar 100° C. heat of fusion 17.8 kJ/g mol 175° C. heat of evaporation 47.2 kJ/g mol 175° C. heat of sublimation 70.2 kJ/g mol 25° C. decomposition point 465° C. magnetic susceptibility diamagnetically ______________________________________
______________________________________ sulfur % by wt. 0.19density 15° C. kg/m.sup.3 839.9 flash point °C. 65 cloud point °C. 2 CFPP °C. -5 cetane number 52.2 boiling situation start of boiling °C. 163 5% °C. 189 10% °C. 204 20% °C. 225 30% °C. 245 40% °C. 262 50% °C. 278 60% °C. 293 70% °C. 310 80% °C. 328 90% °C. 353 95% °C. 370 end of boiling °C. 380 yield % by vol. 99 beg. -250° C. % by vol. 33 beg. -350° C. % by vol. 89 ______________________________________
Claims (17)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4138216 | 1991-11-21 | ||
DE4138216A DE4138216C2 (en) | 1991-11-21 | 1991-11-21 | Process for adding fuel or fuels to ferrocene |
Publications (1)
Publication Number | Publication Date |
---|---|
US5386804A true US5386804A (en) | 1995-02-07 |
Family
ID=6445230
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/978,755 Expired - Lifetime US5386804A (en) | 1991-11-21 | 1992-11-19 | Process for the addition of ferrocene to combustion or motor fuels |
Country Status (7)
Country | Link |
---|---|
US (1) | US5386804A (en) |
EP (1) | EP0543477B1 (en) |
JP (1) | JP3370707B2 (en) |
KR (1) | KR100245839B1 (en) |
AT (1) | ATE133194T1 (en) |
DE (2) | DE4138216C2 (en) |
ES (1) | ES2084271T3 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5823148A (en) * | 1996-05-29 | 1998-10-20 | Housand, Sr.; Raymond W. | Apparatus for introducing combustion supporting particles to an internal combustion engine |
KR100428749B1 (en) * | 2002-03-12 | 2004-04-28 | 한국화학연구원 | New soot-controlling catalytic fuel-additive compositions |
WO2004090319A2 (en) | 2003-04-02 | 2004-10-21 | Rim Julius J | System for and methods of operating diesel engines to reduce harmful exhaust emissions and to improve engine lubrication |
US20050011187A1 (en) * | 2001-08-30 | 2005-01-20 | Cook Stephen Leonard | Composition |
US20060167184A1 (en) * | 2000-10-18 | 2006-07-27 | Waddell Walter H | Innerliners for use in tires |
US20100235073A1 (en) * | 2009-03-13 | 2010-09-16 | Magneti Marelli Sistemas Automotivos Industria E Comercio Ltda. | Sbs logical bio-diesel sensor |
WO2016070746A1 (en) * | 2014-11-05 | 2016-05-12 | 汕头高新区腾力高分子材料科技有限公司 | Automobile oil-saving emission-reducing device and oil saving method |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4138216C2 (en) * | 1991-11-21 | 1994-02-03 | Veba Oel Ag | Process for adding fuel or fuels to ferrocene |
WO2002018398A1 (en) * | 2000-08-31 | 2002-03-07 | The Associated Octel Company Limited | Compositions comprising dimeric or oligomeric ferrocenes |
DE102004025327A1 (en) | 2004-05-19 | 2005-12-08 | Hjs Fahrzeugtechnik Gmbh & Co. Kg | A method for loading a fuel-air mixture with a gas phase additive and apparatus for providing a gas phase additive |
US8101014B2 (en) | 2004-11-10 | 2012-01-24 | Chemetall Gmbh | Process for coating metallic surfaces with a multicomponent aqueous composition |
WO2007080070A1 (en) * | 2006-01-09 | 2007-07-19 | Fraenkle Gerhard Juergen | Method for admixing an additive with a fluid and installation therefor |
WO2008072254A2 (en) * | 2006-11-01 | 2008-06-19 | Bharat Petroleum Corporation Limited | Hydrocarbon fuel compositions |
DE102010038143A1 (en) | 2010-10-13 | 2012-04-19 | Hjs Emission Technology Gmbh & Co. Kg | A method of lowering the soot ignition temperature of soot accumulated on a particulate filter |
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1991
- 1991-11-21 DE DE4138216A patent/DE4138216C2/en not_active Expired - Fee Related
-
1992
- 1992-11-19 US US07/978,755 patent/US5386804A/en not_active Expired - Lifetime
- 1992-11-20 JP JP31243492A patent/JP3370707B2/en not_active Expired - Fee Related
- 1992-11-20 KR KR1019920021850A patent/KR100245839B1/en not_active IP Right Cessation
- 1992-11-23 ES ES92250345T patent/ES2084271T3/en not_active Expired - Lifetime
- 1992-11-23 EP EP92250345A patent/EP0543477B1/en not_active Expired - Lifetime
- 1992-11-23 AT AT92250345T patent/ATE133194T1/en not_active IP Right Cessation
- 1992-11-23 DE DE59205100T patent/DE59205100D1/en not_active Expired - Lifetime
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FR1090321A (en) * | 1953-01-01 | 1955-03-29 | Shell Refining & Marketing Co | Process for the preparation of dicyclopentadienyl iron and its substitutes |
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US4222746A (en) * | 1979-04-25 | 1980-09-16 | Texaco Inc. | Diesel fuel containing wax oxidates to reduce particulate emissions |
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Also Published As
Publication number | Publication date |
---|---|
EP0543477A3 (en) | 1993-08-25 |
DE4138216C2 (en) | 1994-02-03 |
DE4138216A1 (en) | 1993-05-27 |
EP0543477B1 (en) | 1996-01-17 |
JPH05239478A (en) | 1993-09-17 |
ES2084271T3 (en) | 1996-05-01 |
KR930010164A (en) | 1993-06-22 |
JP3370707B2 (en) | 2003-01-27 |
KR100245839B1 (en) | 2000-03-02 |
EP0543477A2 (en) | 1993-05-26 |
DE59205100D1 (en) | 1996-02-29 |
ATE133194T1 (en) | 1996-02-15 |
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